Preparation of detergent compositions



Jan. 18, 1955 G. G. LAUER PREPARATION OF DETERGENT COMPOSITIONS FiledMarch- 25, 1952 uZOlrmv. L

R F. U RA.. OL T NG EE. WG J R.. Imi 0.5. 0C Vl B O Y N 20-03 ATTORNE SUnite PREPARATION OF DETERGENT CGMPOSITIONS Application March 25, 1952,Serial No. 278,400

16 Claims. (Cl. 260-504) This invention relates to a process forpreparing detergent compositions. More particularly, the inventionrelates to a process for preparing sulfonates in the form of salts ofsulfonation products, of high purity and elfectiveness, having detergentand wetting properties, which may be used for laundering and cleansingpurposes in soft or hard water, and which do not leave undesirabledeposits of unreacted materials on the surface of the object which isbeing cleansed.

This application is a continuation-in-part of my prior and co-pendingapplication Serial No. 2,578, filed January 16, 1948, now abandoned.

The use of Water-soluble sulfonates as detergents and wetting agents iswell known. Heretofore', it has been proposed to prepare thesesulfonates by treating mineral and petroleum oils with varyingconcentrations of sulfuric acid, and subsequently neutralizing theresulting sulfonation products with an alkali to obtain watersolublesulfonates, suitable for use as detergent and wet- -ting agents.

It has been found, however, that the reaction of unsaturatedhydrocarbons, in the presence of saturated hydrocarbons, with sulfuricacid or other sulfonating agents for the production of sulfonates orsulfates and their salts, invariably leaves in the product of reactioncertain quantities of unreacted saturated hydrocarbons and/orpolymerized material which are not attacked, even by very highlyconcentrated acids. The presence of these unreacted compounds in thesulfonates thus produced, has resulted in obtaining detergentcompositions of limited cleansing and wetting properties, and consequentlow market value.

It is, therefore, a primary object of the present invention to provide aprocess for preparing improved sulfonates having detergent' and wettingproperties.

Another object of the invention is to provide a process for preparingwater-soluble sulfonates, having the aforementioned properties, which donot leave undesired deposits of unreacted materials when used asdetergent or cleansing agents.

Still another object of the invention is to provide a process forpreparing water-soluble sulfonates, having the aforementionedproperties, from a hydrocarbon feedstock in which unsaturatedhydrocarbons are converted to these sulfonates, substantially free ofunreacted saturated hydrocarbons and other unreacted materials.

With the above and other objects and features in view, the inventionbroadly comprises the improved process of preparing water-solublesulfonates, in the form of a salt of a sulfonation product possessingthe aforementioned properties, by treating a feed-stock comprisingunsaturated and saturated hydrocarbons having from 8 to 18 carbon atomsper molecule with selected sulfonating agents under controlledconditions, to form a reaction product comprising a sulfonated oil; nextcontacting this reaction product with an aqueous solution of a base anda ketone to form a sulfonation salt and unreacted hydrocarbons; andfinally separating the unreacted hydrocarbons by extracting theseunreacted hydrocarbons with a relatively light hydrocarbon treatingagent. In another modiiication of the process of the invention,theaforementioned sulfonation reaction 'product may be contacted with anaqueous solution of a base to form the corresponding salt and unreactedhydrocarbons, followed by contacting the salt with a mixture of thelightv hydrocarbon treating agent and ketone, to effect separation ofunreacted hydrocarbons from the sulfonation product, as more fullyhereinafter described. Particular novelty rates Patent 2,700,052Patented Jan. 18, 1955 ICC has been found to exist in the use of aketone in the process of the invention, either in combination with anaqueous solution of the base in the aforementioned sulfonation step, orin combination with the relatively light hydrocarbon treating agent inthe extraction step, wherein unreacted hydrocarbons are separated fromthe sulfonate. In this respect, I have found that alkali salts of thesulfonation product formed by contacting the aforementioned sulfonatedhydrocarbons with an aqueous solution of a base exert a solutizingeffect upon unreacted hydrocarbons, for the most part saturatedhydrocarbons present in the formed sulfonation product, and hencesubsequent extraction of these unreacted hydrocarbons by means of alight hydrocarbon material is extremely difficult. In adding a ketone,which is water-miscible in combination with either the aqueous solutionof the base or the light hydrocarbon material, I have found that thesolutizing power of the formed alkali salts of the sulfonation productupon the unreacted material is markedly lowered, and hence subsequentremoval of the unreacted material from the resulting sulfonation saltisfacilitated.

Ybeyond the` scope of the apparatus illustrated.

Referring to the drawing, a suitable acid reactive hydrocarbonfeed-stock, such as mineral oil or a petroleum oil hydrocarbon fractioncomprising unsaturated and saturated hydrocarbons having from 8 to 18carbon atoms per molecule, is passed via line 10 into a sulfonation zone11. Sulfonation zone 11, in the drawing, is representative of a reactionvessel or series of reaction vessels or similar conventional apparatus,into which a strong sulfonating agent is introduced through line 12..This sulfonating agent may comprise a strong sulfonation reagent such assulfuric acid having a concentration of at least 80%. Other sulfonatingagents such as fuming sulfuric acid containing approximately 1% to 20%by weight of sulfur trioxide, aceto-sulfuric acid, or chlorosulfonicacid may be used. In all instances, it is preferred to use a strongsulfonating agent of suitable strength which is liquid at the desired.reaction temperature. It should be noted, that the aforementionedreagents such as sulfuric acid or chlorosulfonic acid, etc. are hereinreferred to in their commonly accepted form, as sulfonating agentsregardless of whether they may form true sulfonates or sulfuric acidesters (.sulfates) or mixtures of both, according to the conditions ofsulfonation.

ln sulfonation zone l1, the hydrocarbon-feed intro duced through line10, and the sulfonating agent introduced through line 12, are broughtinto rapid and intimate contact by any conventional contacting means, at

a reaction temperature maintained in the range from about 20 C. to about45 C. in the manner known to those skilled in the art. This sulfonatingstep is preferably carried out at atmospheric pressure but may be alsocarried out at super-atmospheric pressures if desired, within the abovetemperature range. The quantities of sulfonating agent admixed withquantities of Ca to C18 hydrocarbons undergoing sulfonation treatment,may vary from ratios of approximately 1:3 toapproximately 1:1, dependingin each instance upon the quantities of unsaturated hydrocarbons presentin the feed stock. Thus as the quantities of unsaturated hydrocarbonspresent in the feed are increased, the quantities of sulfonating agentsemployed are also proportionately increased. In some instances, it maybe also desirable to add inert diluents to the sulfonating agentemployed, such as ethyl ether or ethylene dichloride. In the latterevent,v the ratios of diluent to the hydrocarbon feed may be relativelyhigh such as 5:1 or even higher. i

From sulfonation zone 1l, the mixture of reactants is withdrawn throughline 13. This mixture comprises sulfonated oils containing unreactedhydrocarbons which consist of either saturated hydrocarbons or bothsaturated and unsaturated hydrocarbons. To the sulfonated oil flowingthrough line 13, there is next added under suitable temperature controleffective to diminish the violence of the reaction, an aqueous solutionof a base and a water-miscible ketone, introduced through line 14 withwhich line 13 connects, in an amount suflicient to neutral- `ize thesulfonated oils (and any excess quantities of the have found that I mayemploy such aqueous solutions of inorganic bases as alkali or alkaliearth oxides, hydroxides, or carbonates. I may also employ aqueoussolutions of organic bases such as trimethylamine, diethanolamine, ortriethanolamine and the like. It should be noted that the dilution ofthe aforementioned bases may be affected not only by the addition ofsuitable quantities of water, but may also be attained by admixture withproper quantities of ice. The use of ice may be desirable in someinstances in order to reduce the violence of the reaction resulting fromthe aforementioned neutralization. As indicated above, the ketoneintroduced with an aqueous solution of the aforementioned base into line13 through line 14, comprises a water-miscible ketone or a mixture ofsuch ketones. While any water-miscible ketone may be successfullyemployed in the aforementioned step to lower the solutizing power of theformed alkali salts of the sulfonation product upon unreacted material,it is preferred, however, to employ ketones or mixtures of ketones suchas acetone or methyl ethyl ketone. In addition,` while the quantities ofthe water-miscible ketone or mixture of such ketones, which is added tothe aqueous solution of` the aforementioned base, may be varied in orderto reduce the solutizing power of the formed alkali salts of thesulfonation product upon unreacted material to the degree desired, it ispreferred, generally, to employ an aqueous solution of the base whichcontains from approximately to 60% of the ketone by volume. It will beunderstood, that in each instance the quantities of the base and ketoneused, may necessarily be varied to obtain optimum neutralizationconditions, accompanied by a sutlicient reduction of the solutizingpower of the aforementioned salts upon unreacted material, asillustrated in the examples hereinafter shown. Ketones admixed with thebase in line 14, are introduced via valved-line 15, with which line 14connects.

In order to effect complete admixture of the aforementioned sulfonationproduct, and the aqueous solution 'I of the base and ketone, thesecomponents are preferably transferred through line 13 to a mixer 16. Inmixer 16 the components are brought into intimate contact for a timesufficient to effect complete neutralization of the,

sulfonation product to form an aqueous solution containing thecorresponding salts of the aforementioned reaction product, ketones andunreacted materials (these materials comprising saturated or bothsaturated and unsaturated hydrocarbons). This mixture is next withdrawnfrom mixer 16 through line 17. In order to facilitate subsequentseparation of the unreacted material, the mixture is next treated with arelatively light hydrocarbon solvent treating agent which is introducedinto line 17, via line 18, in an amount suicient to absorb thereinsubstantially all of the unreacted material. This treating agent ispreferably a low boiling hydrocarbon or hydrocarbon fraction having aboiling point lower than that of the unreacted hydrocarbons which are tobe removed from the aforementioned formed sulfonation salts. Hence, Imay preferably employ such hydrocarbons as liquid propane, butane, orpentane fractions, although higher boiling hydrocarbons or hydrocarbonfractions such as hexane or light naphthas, may also be successfullyemployed. While the proportions of the hydrocarbon treating agent andthe solution comprising the formed sulfonation salts, excess ketones,and unreacted material may be varied, it is generally desirable to addthe hydrocarbon treating agent to the solution in line 17 in a ratio ofapproximately 1:2. At this point, it should be noted that it is possibley as previously indicated to modify the process of the inf. 75 parts ofn-pentane.

vention by introducing the aforementioned water-miscible ketone, orketone mixtures, together with the hydrocarbon treating agent into line17 via line 18, by closing off valvedline 15 and introducing the ketonecomponent into line 18 via valved-line 19. In such event, the quantitiesper volume of the ketone introduced via line 19, may be present in aratio of approximately 1:1 to 1:10 per volume of the aqueous solution ofthe neutralized sulfonation product in line 17.

In order to effect complete admixture of the hydrocarbon solventtreating agent and the constituents in line 17, these components arepreferably transferred into a mixer 20. From mixer 20, this mixture istransferred through line 21 into a settling vessel, represented in thedrawing by separator 22. In separator 22, the mixture is permitted tosettle for a period of time sufficient to effect substantially completeseparation, into an upper oil layer comprising a mixture of thehydrocarbon solvent treating agent and unreacted hydrocarbons, which iswithdrawn through line 23 for further use or treatment outside the scopeof the present process, and a lower layer comprising an aqueous solutionof water-soluble salts of the sulfonation product and the ketonetreating agent, which is withdrawn through line 24. The aqueous solutionin line 24 is next transferred to a stripper 25 (or any conventionalseparation media) which is operated under conditions effective todistill overhead the ketone treating agent which is withdrawn throughline 26. The puried aqueous solution of the aforementioned salts of thesulfonation product is withdrawn as bottoms through line 27 and may betransferred to any suitable storage facilities, or if so desired, can bedried by any suitable means, such as a spray dryer, to obtain thedetergent composition in the solid form.

The aqueous solution of the salt of the sulfonation product in line 27is free of unreacted hydrocarbons and has been found highly suitable asa detergent composition having outstanding detergent and wettingproperties. This detergent is water-soluble, and has been found to haveexceptional efficacy when used for laundering or cleansing purposes ineither soft or hard water, without leaving undesirable deposits ofunreacted materials or foreign matter on the surface or the object whichis being cleansed. It will be understood, of course, that the detergentmay also be used in highly dilute aqueous solutions, depending upon thedegree of cleansing or wetting properties desired.

The following specific examples will serve to illustrate, but are notintended in any way to limit unduly the broad scope of the invention inthe preparation of the aforementioned detergent compositions.

Example I parts of a blend containing chiefly unsaturated Cs-Cishydrocarbons having an average molecular weight of 200 and an iodinenumber of 93 obtained from the product produced in the catalytichydrogenation of carbon monoxide, are slowly added to 50 parts ofcommercially water-free sulfuric acid with constant stirring for severalminutes at a temperature of about 0-20 C. and then poured over ice. Thecooled mixture is next neutralized at a temperature below 45 C. with a40% solution of sodium hydroxide containing approximately 30% acetone byvolume. These constituents are thoroughly mixed and next contacted withapproximately 75 parts of npentane to remove unreacted saturatedhydrocarbons. The treated mixture is then subjected to phase separationto obtain an upper oil layer containing unreacted material dissolved inpentane, and a lower aqueous phase containing the formed sulfonationsalt in admixture with acetone. The aqueous phase is next distilled at atemperature sufficiently high to take the ketone overhead. Thus aslightly hygroscopic material is obtained as bottoms having a yellowishappearance and which is found to possess excellent detergent and wettingproperties.

Example II Example I. The mixture is next poured over ice andneutralized with a 40% solution of sodium hydroxide. These constituentsare thoroughly mixed and contacted with a mixture consisting of 60 partsof methyl ethyl ketone and The treated mixture is next subjected tophase separation .to obtain an upper phase containing unreactedsaturated hydrocarbons dissolved in pentane, and a lower Vaqueous phasecontaining methyl ethyl ketone and a sulfonate in the form of the saltof the reaction product. This `aqueous phase is next distilled at atemperature suciently high to take the ketone overhead, leaving Athesalt as `bottoms possessing properties similar to that of the saltobtained in Example I.

Having thus described my invention, what I claim .and desire to secureby Letters Patent is:

1. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: contacting a feedstock comprising unsaturated and saturatedhydrocarbons having from 8 to 18 carbon atoms per molecule with asulfonating agent containing a free acid group, whereby unsaturatedhydrocarbons are reacted without reacting saturated hydrocarbons, toform a reaction product cornprising a sulfonated oil; contacting saidsulfonated oil with a treating agent comprising an aqueous solution of abase to form a mixture comprising a salt of said sulfonated oil andunreacted saturated hydrocarbons; subjecting said mixture to extractiontreatment with a treating agent comprising a light hydrocarbon to obtainan extract phase comprising unreacted saturated hydrocarbons andhydrocarbon treating agent and a raiiinate phase comprising said salt ofthe sulfonated cil; introducing a water-miscible ketone in combinationwith one of said treating agents in said aforementioned treating steps;separating said extract and rafiiniate phases; and separating said saltof the sulfonated oil fr-om said rainate phase.

`2. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: lcontacting a feedstock produced in the catalytichydrogenation of carbon monoxide comprising unsaturated and saturatedhydrocarbons having from 8 to 18 carbon atoms per molecule with asulfonating agent containing a free acid group at a temperature betweenabout 20 C. and about 45 C., whereby unsaturated hydrocarbons arereacted without reacting saturated hydrocarbons, .to form a reactionproduct comprising a sulfonated oil; contacting said sulfonated oil witha treating agent comprising an aqueous solution of a base to form amixture comprising a salt of said sulfonated oil and unreacted saturatedhydrocarbons; subjecting said mixture to extraction treatment with atreating agent comprising a light hydrocarbon to obtain an extract phasecomprising unreacted saturated hydrocarbons and hydrocarbon treatingagent and a raiiinate phase comprising said salt of the sulfonated oil;introducing -a water-miscible ketone in combination with one of saidtreating agents in said aforementioned treating steps; separating saidextract and raiinate phases; and separating said salt of the sulfonatedoil from said rainate phase.

l3. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: cont-acting a feedstock comprising'unsatura-ted and saturatedhydrocarbons having from 8 to 18 carbon atoms per molecule with asulfonating agent containing a free acid group, whereby unsaturatedhydrocarbons are reacted without reacting saturated hydrocarbons, toform a reaction product comprising a sulfonated oil; contacting saidsulfonated oil with an aqueous solution of a base and w-ater-miscibleketone to form a mixture comprising a salt of said sulfonated oil andunreacted saturated hydrocarbons; subjecting said mixture to extractiontreatment with a light hydrocarbon treating agent to obtain an extractphase comprising unreacted saturated hydrocarbons and hydrocarbontreating agent and a rafnate phase comprising said salt of thesulfonated oil; separating said extract and raffinate phases; andseparating said salt of the sulfonated oil from said raiiinate phase.

4. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: contacting a feedstock produced in the catalytic hydrogenationof carbon monoxide comprising unsaturated and saturated hydrocarbonshaving from 8 to 18 carbon atoms per molecule with a sulfonating agentcontaining a free acid group at a temperature between about 20 C. andabout 45 C., whereby unsaturated hydrocarbons are reacted withoutreacting saturated hydrocarbons, to form a reaction product comprising asulfonated oil; contacting said sulfonated oil with an aqueous solutionof a base and a water-miscible ketone to form a mixture comprising asalt of said sulfonated oil and unreacted saturated hydrocarbons;subjecting said mixture to 4extraction treatment with a lighthydrocarbon treating agent to obtain an -extractphase comprisingunreacted saturated hydrocarbons and hydrocarbon treating agent and araffinate phase comprising said salt of the sulfonated oil; separatingsaid extract and raffinate phases; and separating said salt of thesulfonated oil from said raffinate phase.

5. A process in accordance with claim 4 wherein said base is an alkalimetal hydroxide.

6. A process in accordance with claim 4 wherein said base istrimethylamine.

7. A process in accordance with claim 4 wherein said ibase isdiethanolam'ine.

8. A process in accordance with claim 4 wherein said ketone is acetone.

9. A process in accordance with claim 4 wherein said ketone is methylethyl ketone.

10. A process in accordance with claim 4 wherein said sulfonating agentis sulfuric acid having a concentration of at least 11. A process inaccordance with claim 4 wherein said sulfonating agent comprises fumingsulfuric acid containing from 1 .to 20% by weight of sulfur trioxide.

12. A process in accordance with claim 4 wherein said sulfonating agentis chlorosulfonic acid.

13. A process in accordance with claim 4 wherein said sulfonating agentis aceto-sulfuric acid.

1'4. A process for preparing a salt of a sulfonation product whereinsaid salt possesses detergent and wetting properties which comprises thesteps of: contacting a feedstock comprising unsaturated and saturatedhydrocarbons having from 8 to 18 carbon atoms per molecule with asulfonating agent containing a free acid group, whereby unsaturatedhydrocarbons are reacted without reacting saturated hydrocarbons, toform a reaction product comprising a sulfonated oil; contacting saidsulfonated oil with an aqueous solution of a base to form a mixturecomprising a salt of said sulfonated oil and unreacted saturatedhydrocarbons; subjecting said mixture to extraction treatment with amixture comprising a light hydrocarbon treating agent and awater-miscible ketone to obtain an extract phase comprising unreactedsaturated hydrocarbons and hydrocarbon treating lagent and a raffinatephase comprising said salt of the sulfonated oil; separating saidextract and raffinate phases; and separating said salt of the sulfonatedoil from said rainate phase.

15. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: contacting a feedstock produced in the catalytic hydrogenationof carbon monoxide comprising unsaturated and saturated hydrocarfbonshaving from 8 to 18 carbon atoms per molecule with a sulfonating agentcontaining a free acid group at a temperature between about 20 C. andabout 45 C., whereby unsaturated hydrocarbons are reacted withoutreacting saturated hydrocarbons, to form a reaction product comprising asulfonated oil; contacting said sulfonated oil with `an aqueous solutionof a base to form a mixture comprising a salt of said sulfonated oil andunreacted saturated hydrocarbons; subjecting said mixture 4to extractiontreatment with a mixture compri-sing a light hydrocarbon treating agentand a water-miscible ketone to obtain an extract phase comprisingunreacted saturated hydrocarbons and hydrocarbon treating agent and aranate phase comprising said salt of the sulfonated oil; separating saidextract and raffinate phases; and separating said salt of the sulfonatedoil from said raffinate phase,

16. A process for preparing a salt of a sulfonation product wherein saidsalt possesses detergent and wetting properties which comprises thesteps of: contacting a feedstock comprising unsaturated and saturatedhydrocarbons having from 8 to 18 carbon atoms per molecule with sulfurica-cid having a concentration of at least 80% at a temperature betweenabout 20 C. and about 45 C., whereby unsaturated hydrocarbons arereacted without reacting saturated hydrocarbon-s, to form a reactionproduct comprising a sulfonated oil; contacting said sulfonated oil withan aqueous solution of an alkali metal hydroxide and Iacetone to form amixture comprising a salt of said sulfonated oil and unrea-ctedsaturated hydrocarbons; subjecting said mixture to extraction treatmentwith a light hydrocarbon treating agent to obtain an extract phasecomprising unreacted saturated hydrocarbons and hydrocar- 'bon treatingagent and a raiinate phase comprising said salt of the sulfonatcd oil;separating said extract and rafnatc phases; and separating said salt ofthe sulfonated oil from said raffinate phase.

References Cited in the file of this patent UNITED STATES PATENTSHumphreys Nov. 26, 1918 Ramayya Oct. 17, 1933 Retaillian May 16, 1939Beckham Mar. 7, 1944 Beckham July 25, 1944 Beckham Apr. 17, 1945 FesslerAug. 21, 1945 Showalter Dec. 17, 1946

1. A PROCESS FOR PREPARING A SALT OF A SULFONATION PRODUCT WHEREIN SAID SALT POSSESSES DETERGENT AND WETTING PROPERTIES WHICH COMPRISES THE STEPS OF: CONTACTING A FEEDSTOCK COMPRISING UNSATURATED AND SATURATED HYDROCARBONS HAVING FROM 8 TO 18 CARBON ATOMS PER MOLECULE WITH A SULFONATING AGENT CONTAINING A FREE ACID GROUP, WHEREBY UNSATURATED HYDROCARBONS, ARE REACTED WITHOUT REACTING SATURATED HYDROCARBONS, TO FORM A REACTION PRODUCT COMPRISING A SULFONATED OIL; CONTACTING SAID SULFONATED OIL WITH A TREATING AGENT COMPRISING AN AQUEOUS SOLUTION OF A BASE TO FORM A MIXTURE COMPRISING A SALT OF SAID SULFONATED OIL AND UNREACTED SATURATED HYDROCARBONS; SUBJECTING SAID MIXTURE TO EXTRACTION TREATMENT WITH A TREATING AGENT COMPRISING A LIGHT HYDROCARBON TO OBTAIN AN EXTRACT PHASE COMPRISING UNREACTED SATURATED HYDROCARBONS AND HYDROCARBON TREATING AGENT AND A RAFFINATE PHASE COMPRISING SAID SALT OF THE SULFONATED OIL; INTRODUCING A WATER-MISCIBLE KETONE IN COMBINATION WITH ONE OF SAID TREATING AGENTS IN SAID AFOREMENTIONED TREATING STEPS; SEPARATING SAID EXTRACT AND RAFFINATE PHASES; AND SEPARATING SAID SALT OF THE SULFONATED OIL FROM SAID RAFFINATE PHASE. 